Beneficiation of gases and vapors



SePt` 2, 1958 w. w. ODELL l BENEFICIATION OF' GASES AND VAPORS Filed Jan. 20, 1955 Unired States Patent BENEFICEATION'OF GASES AND VAPRS Wiiiiam W. Odell, Amherst, Va. Application `anuary 20, 1955, Serial No. 483,152

8 Claims. (Cl. 23a-i3) This invention relates to the beneciation of gases and vapors. ln particular it has to do with a substantially continuous process of improving the chemical characteristics of a gasiform fluid as it passes through and in contact with a pervious deep mass of Contact solids while maintaining a hot zone in said mass intermediate top and bottom cooler zones thereof. Still'more specifically the invention relates to the alteration of sulfur compounds in a gasiform fluid initially containing one or more of said compounds by thermal and/or chemical reactions promoted in said iluid as it passes rapidly serially through a relatively cool zone, a hot zone and another relatively cool zone in contact with small-size contact solids disposed as a deep continuous bed in a reaction chamber.

This invention is a continuation in part of my applh cation Serial No. 670,409, led May 17, 1946, subsequently retiled as a continuation application Serial No. 266,614 on January 16, 17952, now Patent No. 2,700,600, dated January 25, 1955, and Serial No. 266,738, also tiled January 16, 1952, `for treating gases, now Patent No. 2,731,335, dated January 17, 1956. The present application relates in particular to the zalteration of sulfur compounds initially present in a gaseous iluid, commonly as an impurity in small percentage amounts.

One of theV objects of this invention is to alter the chemical composition of sulfur impurities in combustible or other gasiform or vaporous fluids through contact with hot solids under such conditions that the luid reaction products are immediately cooled upon leaving contact with said hot solids, whereby high-temperature equilibrium is largely preserved and reverse reactions are not promoted.

Another object is the production and recovery of elemental sulfur from gasiform uids initially containing Vconvertible sulfur compounds. Still another object is the purification of impure gasiform iluidszor vaporous iluids by conversion of thefmpurities by chemical reaction in the presence of an oxidizing iluid at elevated temperature by passing a stream initially containing said impurities longitudinally through an elongated mass of small-size solids having a heated portionV intermediate the cooler ends thereof, whereby reaction products, formed in the hot zone are so rapidly cooled in a downstream cooler and zone, that they are not appreciably further reacted in the reactor. Manufactured gases such as oil gas, carburetted water gas, synthesis gas containing organic and/or inorganic sulfur compounds are examples of gases adapted for treatment.

Other objects will become apparent from the disclosures hereinafter made.

ln the manufacture of ordinary water gas, for example, the maior components are hydrogen and carbon monoxide in the respective amounts of about fty and forty percent. However, besides these components there are present, usually, small amounts of impurities such as H28, CS2, thiophene, mercaptans, organic sulphides, hydrogen cyanide, olens, diolens, methane and other undesired materials. ln present practice the H25 is largely removed by absorption in water, an alkaline solution, or by reaction with iron oxide. Organic sulfur is largely removed in common practice by absorption in active carbon or oil washing. One known procedure for removing organic sulfur is by contacting the gas with a catalyst comprising thirty percent sodium carbonate and approximately seventy percent iron oxide; the reaction being conducted at about to 200 C. In the latter operation the sodium carbonate is converted to sulphate andvthen new catalyst is required. So far as the inventor is aware a truly satisfactory procedure for reacting sulfur-compounds and the gum-forming components has not heretofore been provided. In the practice of this invention an economical procedure is provided in which vcatalyst need not be thus consumed and one which does not require separate heat exchangers to economize the sensible heat of the exit gas, For highest degree of purication and conversion it is usually preferable in the practice of this invention that the gas treated be first subjected to a rough or so-called coarse purification for the removal of the major portion of the H28, particularly if the gas to be treated initially contains large amounts of it.

This invention is particularly applicable to the treatmeut of gases at high temperatures preferably in the presence of steam or other endothermie oxidant and a relatively small amount of oxygen, whereby the desired conversion or decomposition of impurities is accomplished.

One form of apparatus in which this invention may be practiced is shown diagrammatically, in elevation in the figure which in essence is a ilow diagram.

ln the ligure the reactor l connes a deep bed of small-size solids'Z supported on grate 3. Reactant fluids to be introduced into the reactor 1 are supplied through conduit 4 and valves 5, 6, '7, 8 and 9, whereas recycle gas is supplied through valve 3l. The fluids chosen, and passing through conduit e, are mixed in mixing chamber 10 and pass through the control valve 11. During one period ofv operation the huid stream from 11 passes through conduits 16 and 17 to the bottom of the reactor 1 and thence up through grate 3, bed 2, and out through valve 19, conduits 20 and 2i, and valve 22 to producttreating plant 23. The products not extracted in the latter plant exit through pipe 24 and valve 25 except the portion which is used for recycle, which passes through valve 28, conduit 29, pump 30 and valve 31. Fuel may be supplied to the top and bottom of the bed respectively through valves l2 and 14, and combustion supporting uid may be introduced through 13 from above and through i5 from beneath the bed. The hot zoneshown yat H travels alternately upwardly and downwardly during operation, having a top during upward blasting of the reactants at about AB below the top level of bed 2, and having a bottom above the grate at about CD at the end of the down blast period of operation. Gaslform or vapor-ous hydrocarbon substance, combustible gas or other uid containing sulfurous impurities are admitted through valve 5. The iluids admitted through valves 6, 7, S and 9 are, respectively, CO2, steam, air or oxygen, and gas containing H25. Sulfur is removed from treating plant 23 through valve 32. During the down-blast period valve 11 is so positioned that the uid stream passing therethrough passes serially through 16-A, 13, bed 2, 3, 17, 26, 27, 21, 22, 23, 2d and The recycle gas travels, as with tip-blasts, from 23 through 28, 29, pump 30 and valve 31. The stackgas formed during the initial heating period exists through valve 33. One method of igniting the fuel burned in the reactor during the heating up period is by inserting burning com- Ybustible matter through ignition doors 35 or 34, according 'as the mltial blasting is down or up through the bed. The temperatures of different vzones in the rei actor are determined Yby the use of thermocouples 36,

37, 38 and 39 which are suitably connected fortemperature recording. Y- I EXAMPLE 1Y Y i -i Conversion of organic sulfur initially Vpreseritn a thesis gas comprising essentially CO and H2'. Y

Before treating the synthesis gas a hot zone is established 1n bed 2 either as shown in the parentcases orras follows: A gasiform fuel and air for its combustion are admitted at one end of the reactor, say through 12 and 13,

respectively, and the fuel is ignitedY as Vthrough ignition Ydoor l35. The products of'cornbustion are passed down through bed 2, exiting at the bottom of reactor i1, and

are passed through 17, valveV 26, conduits 27 and'21 and out through valve 33 to the stack. This heating operation is conducted until an appreciable layer ofthe Solids three to six feet in bed 2 adjacent the top are heated to a temperature of about 1600 to 1800"V F. During this heating operation Vit is desirable to increase the amount of air overheating the top layer of solids. Now the fuel valve V12 1s closed and air blasting is continued forl a short period,.which causes the hot zone to travel downwardly progressively, using an excess of air, in order to avoid below about AB. Now the air valve 13 is closedV and the Y n The synthesis Vgas is supplied through line 4 and valve S and a small relative amount of oxygen, in this example 1.2 per cent by volume of the synthesis gas fed to the reactor,

is introduced throughV valveV 8. The combined stream Valong with steam admitted through valve 7V is mixed in mixing box 10 and passes through valve 11, conduits 16,-A and V18, andY down through bed 2, passing first through then passing through the incandescent hot zone and immediately through the relatively cool bottom zone. The thus treated gas passes out of reactor 1 through conduit rbed is in condition for the gas-treating operationy to begin. Y

the relatively cool top zone, Vbecoming preheated, and

17, valve 26, conduits` 21', 27 Vand valve 22, plant 23 and Y nally through 24 and valve 25, The operating data are:

Organic sulfur in synthesis feed -gr. per 100 ft 12 Temperature of Vsynthesis gas fed to 1 F' 300 Temperature of oxygen supplied FL- 220 Pressure in the'reactor lbs. gage 60 Y Rate of feed of synthesis gas to reactor based on normal temperatureand pressure is 5 cu. ft. per sq; ft. area of reactor (through AB) per second. Oxygen used, 1.2% of the synthesis gas. Y Steam used, approximately 5 lbs.V per M. c. f. of syn thesis gas (100 cu. ft).

Downblasting is continued until the bottom ofthe hot zone'has moved down to CD and the temperature of the gas discharged through 17 'is 300 to 400 F. Thermo-Y couples 38 and 39 are helpful in determining Ythe change point. The valve 11 is now turned, valve 26 is closed and valve 19 is opened andan up-blast run is promoted in a Vlike manner as the downblast, until the temperature of vthe exiting gas is 300 to 400 Fand then the cycles are kone inch mean diameter in this example.

The processis` continuous but the operation is cyclic as to change of direction of flow of fluids through'theV reactor. The solids of bed 2 are A1203 in the foregoing Y example but may beA SiQz, or Cr2Q3, silicious pebbles, or

manufacturedk refractory solids. Ihe amount of oxygen used is always such thatthe temperature is maintained at the chosen degree in the hot zone. Under some conditions, depending on the nature of the hot zone (depth) and the kind of organic sulfur compounds present, lower temperatures than given in theY foregoing example may be employed. This can be determined by test.

EXAMPLE 11 Removal of organic sulfur, gum-forming diolens and reduction of methane contentfof water gas made Yfrom coal, coke and the like, composed chieyof H2 and CO but containing approximately 1.8 per cent of CH4 and 0.2 per cent of illuminants which latter includes the gum forming constituents, and 8 grains per 100 cubicgfeet of organic sulfur compounds. Y

Chamber 1 is lled with carefully selected solids,rpref erably about one inch mean diameter in large .reaction Ychambers and preferably spherical, which may be chieiiy Si02, A1203, Cr2O3 or other highly refractory material.A Thejsize of the solids should preferablyV beappreciably smaller than one inch mean diameter in small size reactors.

Combustible fuel gas (the water gas to be treated isV satisfactory) is caused to ow through 4 by opening valve 5,' 1

and van excess of airY forits combustion is admitted Yby opening valve 8. Valve l11 is so opened that the gas flows through 4, 10 and,11 and conduitklo-A to the top of 1,

Vwhereit is burned with air. The mixture thus burned in -1 after it is ignited,`as through ignition port 35. Com-k bustion is continued and the air and gas ratios varied so vthat an appreciable thicknessof bed V2 is heated to'1800 to 2300V F., meanwhile removing'tle products of Vcombustion through 1.7, 26, 2,7, 21 and 33, valves 19 and 22 being closed. n The gas valve 5 is now closed and astraight air blastris made, removing the air similarly through 17,`

26, 21 Yand 33. The solids in the lowest zone of 1 'Will now be atV about Vatmospheric temperature, `a higher zone is now the hot zone in 'which the solids are heated to 1800 to about 23.00 F., and the top-zone solids` are at substantially 300 to 400 F. 'Ihe apparatus ofthe figure is now Y ready for regular operation. Y Valve 272'is now opened and f Y Yvalve 33 is closed. Water gas is admitted'by opening Y valve 5; steamY is introducedby opening valve "I, and a very small amount of A`oxygen or air is admitted by opening valve 8. The selection of 022er air is madechieiiy' in accordance with the `requirements .or limitations.y as Vto nitrogen content of the finished gas, If oxygen is used me amount, which 'may vary Ywith diierent kindsof waterY gas from 0.2 to 5 per cent or more, should be, in this example case, about products pass out at the Ybottoni of 1, through'1726',27, 21 and valve 22 tothe gas handling system 23,1y This 1s continued until the temperature of the gas stream leaving the bottom of the reaction chamberf1- reaches approximately 300 `tor400" F. The 'operation is continued but the direction of ow of uids through lis now reversed,y Abyreversing valve 11"and substantially simultaneously closing valve 26 Vand'opening valve 19; YThe Vcourse of the gas stream from'valve 11V isV now through 16, `17bed'2, 18, valve 19, lines'20` and reaches about 300 to '4009' F. another reversalof ow through reaction chamber 1 is initiated. The process is continuous kand the temperature is self-sustaining andthe heat wave or hot` zone travels alternatelyA upwardly and downwardlythroughthe bed of solid 2. It'may-be desirable at infrequent time intervals (periodically) Vto make a prolonged airiblast to the'stack by'closing valve 22 and Y opening valves 8 andf 33, allowing the outlet blast gas temperature to rise above said 300 to 400 F. and admitting a small amount of gas through 4, 5, 10,11, 16 and 17 during a late stage of the air blast period. The gasair mixture at this stagemay lne-one volume of gas and fifteen to twenty volumesofwair. Y

1.0 pei cent. The resulting gaseousY 21 y'and'valve 22 to the treating plant 23. VWhen the temperature ofthe outlet-'gas from 1 Y -cordance with the diameter of the reaction chamber.

aseea During the regular gas-treating operation the proportions of O2, gas and steam used in this example are:

The pressure in the reaction chamber and system may be substantially atmospheric pressure or to 20 atmospheres or more may prevail. One of the advantages of the use of superatmospheric pressure is that smaller equipment and lower linear velocities through the Contact solids may be employed. Somewhat more steam is desired Vwhen operating under superatmospheric pressure than at atmospheric pressure, particularly When the feed gas contains hydrocarbons, to prevent carbon formation, although 200 cubic feet of steam per 1000 .cubic feet of water gas is usually ample even at atmospheres pressure. There is no apparent advantage in appreciably preheating the gas or oxygen but the steam used should be at such a temperature relative to the oxygen and water gas that condensation of Water vapor does not occur in the linlet conduits to the reaction chamber; the steam-gas mixture may enter the reaction chamber somewhat below 200 F. The linear velocity of the fluid stream into the bed of vsolids in the reaction chamber, calculated as at 60 F., may be of the order of 100 to 500 cubic feet per minute per square foot of equivalent grate area, namely per vsquare foot of internal horizontal sectional area of said chamber.

The `size of the solids used should be selected in ac- A ySize yof about 0.75 to 1.5 inches mean diameter is satis- 'factory for large lchambers having an internal diameter of 8 to 10 feet, lWhereas With `chambers 4 to 5 feet internal .diameter the size solids preferred is 0.6 .to 1.2 inch. Although the `solids should be as uniform in size as possible in order to minimize the wall effect and to minimize the necessity of ,periodically driving the heat to substantially one end of the reaction chamber, it is decidedly :advantageous to employ metal spheres Vor the like `at the Vtop and bottom layers and these can be smaller than lthe other solids. The kmetal vbeing-a better conductor of .heat than the oridinary refractory solids is perhaps an lexplanation of the leveling out effect of the metal solids on .the temperature in the end zones. The temperature zones should be horizontal layers; the use of .metal in the -top and bottom layers is :helpful in maintaining this condition.

The results obtained in this vExample II are indicated by :gas analyses as follows:

Composition of the moisture free gases The Ygum forming hydrocarbons which were present Vin the raw -water 4as Awere entirelyeliminated and the volume of combustible `gas Wasincreased l4 percent. Apparently oxidation andre-forming reactions occur in the reaction chamber in avery efcient manner. -Some 0f these reactions Which'can'occur aref' Dioleins polymerize, split, oxidize and also react With hydrogen to form saturated hydrocarbons which in turn are re-formed by reaction with steam to form CO and Hg or with O2 to form CO and H2. Likewise reaction 6.pro ceeds at quite low temperatures. Thus small amounts of hydrocarbons may be eliminated and the total volume of CO-l-Hz increased simultaneously with the elimination of nitrogen oxides and gum-forming substances.

The invention is not limited as to the velocity of flow of iiuids through the bed of solids. However, the time of contact of the uids with the hot solids Vwill vary according to the temperature of the solids and the nature of the gas being treated. Experiments with a given gas at a chosen temperature will establish a possible limit.

'Equations 6 and 8 are for endothermic reactions and are favored by high temperatures, Whereas the reaction of Equation 7 is highly exothermic and usually occurs before the zone of maximum temperature is reached because of the low ignition temperature of CS2.

fThe'temperatures given in the example are'those found to be satisfactory without the use of catalyst solids. Oxidation catalyst can be used at lower temperatures, particularly with some gases. Thiophene and some rgum formers are best destroyed by high temperature treatment as described.

Coal gas or mixtures of water gas and coal gas may be similarly treated and the sulfur compounds therein converted.

It will be noted that the stream initially containing the reactant fluid, in passing through the bed of prepared small size solids, as in reaction chamber 1 of the figure, first contacts relativeiy cool solids and as its travel continues its temperature is raised, layer by layer, to the maximum temperature in the hot zone of said bed and is then similarly cooled to a similar lower temperature. As the stream temperature rises in its travel through the bed it reaches a temperature where reactions such as shown in Equations 6, 7 and 8 occur at a much faster rate than the steam hydrocarbon reactions, and this is a very desirable condition; the hydrocarbon endothermic reactions proceed rapidly only at higher temperatures, above about 1650 F. without a catalyst. Therefore, in promoting chemical reactions in a gas stream by this invention the oxidation of the'hydrocarbons by oxygen is initiated before the oxidation of hydrocarbons by CO2 or steam. Heat is thus provided to maintain the desired temperature of the intermediate hot zone of the bed.

In most processes, so far as I am aware, the substitution of CO2 for steam as a reactant for hydrocarbon conversion is not particularly Vadvantageous since the heat required is substantially the same in each case, i. e., Equations 3 and 5. However, in this invention, and in the preparation of a synthesis gas for example, CO2 is usually Washed Iout of the raw gas made and is discarded. Its use in this Vinvention is indicated to the extent it is available and to the limit placed by any particular ratio of H2 to CO in the synthesis gas. Lower reactor inlet and outlet temperatures can be used in this invention when CO2 is employed replacing an equivalent of steam. They may be as low as 60 to 100 F.; condensation is not then a factor.

A catalyst may be used in any portion of the bed or the bed may -be comprised substantially entirely of cata- F. to l850 F. usually may be employed, a range found t to be Satisfactory and sometimes preferred is above about A lower temperature than 1800" F., say l200 Yto 1600" F. is advantageously employed, for example, when treating oil-gas having an appreciable' content of oleiins to about 25%) with some diolens, organic sulfur and other impurities in Vlesser amounts. In this instance the steam employed functions to preserve the more stable hydrocarbons, such as methane, ethane, propane, ethylene,Y benzene and the like, in this temperature range,

while the less stable CS2, dioleiins and'high-molecularweight hydrocarbons are readily converted. The CS2 having a low ignition temperature is usually oxidized before other reactions are completed, by such reactions as indicated by Equations 6 and 7. It will be noted that vSO2.reacts with 2H2S to form sulfur and water vapor.

Yby Van exothermic reaction; this reaction isV not favored by extremely high temperatures or -by the presence of steam, hence the SO2 formed in this process at reaction temperatures below l600 F. inthe presence of added steam does not immediately react with H2S forming free sulfur. The latter reaction occurs after, the stream `of reactants has cooled, usually after the streamof reac- Vtion`products exits from the reactor; the sulfur'Y is recovered by known means from the exit gas stream in the producttreating plant. n

l EXAMPLE In Converting jH2S, commonly present in the Yeffluent fluid Ystreams from a gas-purification-plant'regenerating-system;

and'producing sulfur. l

The basic reaction is typified by Equation 14 as follows; Y Y

This is a highly exothermic reaction. The gasitreated in this example has a composition (dry basis) as follows:

. Percent YThe gas is mixed with 25.0 cubic feet of oxygen Vas airY (1,20 feet) per 1000 cubic feet, and with 2 lbs. of steam and pased through the reactor as a'stream.V Referring to the gure operation isY as follows: A hot zone H is 'established in bed, 2 as describedrwith a temperature of about e 1350 F. The gas to be treated enters the system fromf4 -by openingvalve 5; the oxygen (air) and steam are introduced by opening valves 8 and 7 respectively. The

vthrough valve 32. In thisY example a little moreheat isY released in the reactor by thel oxidation of the H2S toS Vand H2O than is required to maintain the chosen temperature of 1350 F. in the hot zone. Under theseY conditions it is expedient to'introduce the mixture at as 'low a temperature as feasible and to allow each run (upland t down) to continue until the temperature `of the gas stream exiting through 18'and 17 respectively is at a temperature about 300 F. higher than the feed-mixture temperature. Operating data are substantially as follows;

Temperature of the feed mixture Fl.- 100 Final temperature of the exit gas as indicated by thermocouples 35 and` 39 F 400V Relative proportions of reactants in the mixture supplied to reactor 1 are:

Gas containing H2S -cubic feet.. 1000 Air do 120 Steam Y pounds 2 Pressure in system, slightly above atmospheric. Rate of feecl'of mixture to reactor, cubic feet per second per square foot area of section of 1 Y through AB or CD All of the H2S of thefeed gas is reacted.

Under the chosen hot Vzone temperature it isV quite necessary to dissipate' heat, as Vnoted above, in `orderkto maintain satisfactory operating conditions. Operating as Yin this Example IIIl the sulfur formed is carried out of the reactor in the vapor phase in the stream conveying-reac- .tion products. -Treating gases containing a greater-perfY feedgas is higher than can conveniently be converted in the reactor withsatisfactory temperature control the spent gas (residue after the extraction of sulfurin theproduct treating plant 23) is recirculated back tothe reactor in amounts required. The recycle gasV thus returnedis conductedfrom 23 through valve 28, conduit 29 and pump ..30 to mixing chamber 10. By the use of recycle gas the EXAMPLE IV Y Conversion of sulfur compounds initially present in oilV gas which gas has a'highrthermalY (caloric) .value Referring to the` figure, a hot zone `is established at H of the gure, having a temperature'of1350 Y1to'1500 F. in a manner substantially as described. The gasto be follows:

stream of themixture pases through 1,0 and 11, and then alternately down for a period and then up fora period, Vpassing through Vand in Contact with the mass of Vhot solids in zone H during each run. The productV gas passing' on through line 2l and valve 22 to the treating plant 23 in each case, and the sulfur formed during processing inthe' Carbon dmndp 2 0 Carbon monoxide 'Y 1;4 Hydrogen 26.1 VEthylene`V 22.1 VMethane 36.8 Ethane V5.1 Propane 1,0 Propylene .3 4 Butane Y0.3 VButylene i 0.1V f Butadiene 0.

treated in this example as a composition 'substantially as Vol. percent Y Cyclopentadiene 0.3 Acetylene 0.2 Nitrogen 0.3

Organic sulfur, grains per 100 cu. ft 54 `B. t. u. per cubic foot 1056 The gas of given composition is introduced from line 4 by opening valve 5 and the oxygen and steam are supplied by opening valves 8 and 7. The amounts of oxyg'en and steam supplied per 1000 cubic feet of the oil gas are, respectively, 17 cubic feet and about 3 pounds. The superficial velocity of the stream in the reactor is high, being of the order of 5 to 10feet per second. It is found that as the temperature rises appreciably above1400 F. increasing amounts of hydrocarbons are converted, by reaction with steam to CO, CO2 and H2 by endothermic reactions, and this feature is helpful in maintaining the desired temperature in the hot zone. More oxygen is required at higher temperatures than about 1400 F. and at low rates of fluid dow through the reactor, in order to maintain the temperature inthe hot zone, when hydrocarbons are present in appreciable amounts in the uid under treatment.

2 The composition of the treated oil gas in this VExample IV is as follows:

Vol. percent Somewhat summarily it may be said that the nature of the refractory solids and their size are chosen to suit conditions. They should be substantially non-reactive with sulfur, of high melting point and resistant to spalling.

Temperatures in the hot zone and the depth of the hot zone are chosen with reference to the nature and properties of the fluid treated, so as to avoid undesirable side reactions. Water gas and the like can be treated at high temperatures with a deep hot bed 5 to 8 feet or more and, when desired, a low ow rate can be safely employed, but when treating a gas or vapor containing hydrocarbons which are desirable in the finished product it is advisable to employ high flow rates and a relatively thin hot zone. The amount of oxygen used is sucient to maintain the temperature in the hot zone and to oxidize the organic sulfur initially present in the fluid under treatment. Very little oxygen is required ordinarily.

Referring again to Equations 6 and 7, column 6, it will be noted that the oxidation of CS2 to H28 and CO2 is endothermic and is favored by excess steam and high temperatures, whereas the reaction typified by Equation 7 is highly exothermic and occurs at low temperatures. In promoting both of these reactions together it is possible to so adjust the relative amounts of steam and oxygen so that the H28 and SO2 formed are in the approximate proportion whereby the reaction to form elemental sulfur, as indicated in Equation 14, may occur, namely 2 vols. of H28 to 1 vol. of SO2. These substances in thefluid discharged from the reactor are then, at a lower temperature than thatY of the hot zone, allowed to react with the formation of sulfur-which is recovered.

For a wide range'of uids to be treated the bed depth in the hot zone (the thickness of the hot zone) is within the limits 2 to 8 feet although the invention is not 'thus limited. Because the rate of cracking of hydrocarbons increases rapidly with increase in temperature it is important when treating hydrocarbon vapors and/or gases to coordinate the temperature and duration of contact with the hot solids. A shorter time of contact is usually required at the higher temperatures and to bring about this condition a thinner hot zone may be used or a'higher superficial stream velocity maybe employed, or both may be used. Additional steam dilution is also helpful until a temperature is reached where an'excessive amount of steam-hydrocarbon reaction occurs. Itis understood that superatmospheric pressures may be employed in promoting reaction in ythe reactor. The temperature of the feed stream to the reactor is a governing factor as to a limiting pressure; that is, the pressure must not be so high that one ormore components of the feed stream condenses in the reactor inlets. Again, when air is used as the combustion supporting fluid it must be compressed to the chosen pressureas must also the fluid to be treated. Pressures up to .about 500 pounds are in general satisfactory. Y

Having described my invention so that -one 'skilled in the art can practice it without limitation to the specific examples and shape of apparatus, I claim:

1. A process of beneciating a uid selected from the class consisting of combustible gases and vapors initially of low carbon dioxide content which contain small amounts only of readily oxidizable sulfurous compounds and altering the chemical nature of said compounds at elevated temperatures, comprising, passing a stream initially comprised of such a fluid, containing gasiform combustible matter, with a relatively small amount of free oxygen, and an oxidizing substance, selected from the class consisting of steam and CO2, substantially longitudinally through a confined, continuous, elongated mass of small-size refractory solids while said solids are at an elevated reaction temperature below 2300 F. in a hot zone thereof intermediate much cooler end zones, whereby said stream is preheated in the inlet end zone, heated to reaction temperature in said hot zone and immediately quickly cooled to a much lower temperature in the exit end zone of said mass, thereby altering the chemical composition of said compounds in said stream by oxidation in contact with the hot solids, meanwhile maintaining the said reaction temperature in said hot zone by burning some of said combustible matter initially present in said stream with the said free oxygen, and recovering the cooled, beneficiated fluid exiting from the exit end zone of said mass as combustible gas.

2. A process of beneiiciating a fluid selected from the class consisting of combustible gases and vapors initially of low carbon dioxide content which contain small amounts only of readily oxidizable sulfurous compounds, and altering the composition of said compounds, comprising, passing a stream, initially comprising such a fluid containing combustible matter, a small amount of a combustion supporting gas and a small percentage amount of an oxidizing medium selected from the group consisting of CO2 and steam, in cycles upwardly and downwardly completely through an upright, conned, continuous, deep bed of small-size refractory solids, which bed has a hot zone intermediate the relatively cool top and bottom zones thereof at a reaction temperature of the order of 1250 to 1800 F., thereby causing said stream to be preheated in the inlet end of said bed, to be heated to reaction temperature in said hot zone for a period suf cient to alter the composition of said sulfurous compounds, and to be immediately quickly cooled to a much lower temperature in the exit end zone of said bed, meanwhile maintaining the said temperature in said hot zone by promotingethe combustion of combustible matter ini- ',tially present in said stream with said combustion supof the hot zone is maintained at 2 to 8 feet.

Y4 .j'I'he process delined in claim 2, in which'the sulfurous compounds Aare oxidized at least inpartto free Y sulfur and in which'the sulfur i's'r'er'noved from said mass Vin kthe vapor phase in said stream and recovered.

5. The process defined in claim 2, in which some of the Vproduct. gas freed of elemental sulfur is recycled to the mass along with said stream as a method YofV controlling Ythe temperature in the hot zone, preventing overheating.k

-6.' The process dened in claim 2,in which the said stream initially also contains hydrocarbon substance and in Whichrendothermic lreactions of some of said substance with an oxidizing medium is promoted as afmearisY of preventing overheating of the hot zone. l

7.`The` process dened in claim 2, inrwhich the stream initially containing sulfurous gases to be reacted is treated Y Y the lmass of Solids while yunder pressures of l to 500 pounds per square inch.

8. A process'of beneciating a fluid selected from the Yclass consisting of combustible gases and vapors initially Yof low carbon dioxide content which contain small n amounts only of readilyY oxidizable sulfurous compounds Y at elevated temperatures, comprising, mixing fscha gas Y vand Vto be immediately quickly Vcooled to a much lower with steam and with a gas containing free oxygen, passing the mixture as a stream alternately upwardly and downwardlyV completely through an upright,j connd,

deep, continuous bed of small-size refractory solids, which Y fbed hs'a hot/zone, intermediate top and bottom relatively cool end zones, at a temperature of the order of125.0 F. to 2300" F., thereby causing said stream Vto bepre-V .heated'in the'inlet end zone of said bed, to be heated ,tot

reaction temperature in Ysaid hot zone for a vperiodisufcient to alter 4the composition of said sulfurouscom- Ypounds in said ystream by incomplete; oxidation thereof,

temperature in the exit end zone. of` said bed, meanwhile maintainin'gtlieV saidV temperature Vin said hot zonelby 15 promotingrthe combustion therein of combustible matter Yinitially present in said stream withsaid ffreeloxygen,

and recovering the cooled, beneficiated uid exiting fromv Y Vthe exit end zone of said massas combustible gas. 20 i ReferencesCited in theV le Vofthisrpatent il UNrrED srATEsPATNTs v 1,941,702 Maier 2,1934 2,044,960 Tryer .Lt..` ..-June 23, V,1936 V25; '2,389,810 oneu et a1. V Nov, 27, 1945 2,421,744 Daniels et al. V June10, 17947 VV2,642,338 Pike V Jan. `16,/ 1953 ODell a Jan. 17, 1956 

1. A PROCESS OF BENEFICIATING A FLUID SELECTED FROM THE CLASS CONSISTING OF COMBUSTIBLE GASES AND VAPORS INITIALLY OF LOW CARBON DIOXIDE CONTENT WHICH CONTAIN SMALL AMOUNTS ONLY OF READILY OXIDIZABLE SULFUROUS COMPOUNDS AT AND ALTERING THE CHEMICAL NATURE OF SAID COMPOUNDS AT ELEVATED TEMPERATURES, COMPRISING, PASSING A STREAM INITIALLY COMPRISED OF SUCH A FLUID, CONTAINING GASIFORM COMBUSTIBLE MATTER, WITH A RELATIVELY SMALL AMOUNT OF FREE OXYGEN, AND AN OXIDIZING SUBSTANCE, SELECTED FROM THE CLASS CONSISTING OF STEAM AND CO2, SUBSTANTIALLY LONGITUDINALLY THROUGH A CONFINED, CONTINUOUS, ELONGATED MASS OF SMALL-SIZE REFRACTORY SOLIDS WHILE SAID SOLIDS ARE AT AN ELEVATED REACTION TEMPERATURE BELOW 2300*F. IN A HOT ZONE THEREOF INTERMEDIATE MUCH COOLER END ZONES, WHEREBY SAID STREAM IS PREHEATED IN THE INLET END ZONE, HEATED TO REACTION TEMPERATURE IN SAID HOT ZONE AND IMMEDIATELY QUICKLY COOLED TO A MUCH LOWER TEMPERATURE IN THE EXIT END ZONE OF SAID MASS, THEREBY ALTERNING THE CHEMICAL COMPOSITION OF SAID COMPOUNDS IN SAID STREAM BY OXIDATION IN CONTACT WITH THE HOT SOLIDS, MEANWHILE MAINTAINING THE SAID REACTION TEMPERATURE IN SAID HOT ZONE BY BURNING SOME OR SAID COMBUSTIBLE MATTER INITIALLY PRESENT IN SAID STREAM WITH THE SAID FREE OXYGEN, AND RECOVERING THE COOLED, BENEFICIATED FLUID EXITING FROM THE EXIT END ZONE OF SAID MASS AS COMBUSTIBLE GAS. 